Australia Falref

1DWLRQDO3ROOXWDQW,QYHQWRU\
Emission Estimation
Technique Manual
for
Alumina Refining
First Published in March 1999

EMISSION ESTIMATION TECHNIQUES
FOR THE
ALUMINA REFINING INDUSTRY
TABLE OF CONTENTS
1.0 INTRODUCTION ................................................................................................. 1
2.0 REPORTABLE SUBSTANCES............................................................................ 2
3.0 EMISSION ESTIMATION TECHNIQUES...................................................... 4

3.1 Use of Emission Factors................................................................................ 5
3.2 Mass Balance Techniques ............................................................................ 5
3.3 Software Models ............................................................................................ 6
4.0 LOCATING EETS IN THIS MANUAL............................................................. 7
4.1 Assessing Emissions from Your Facility ................................................... 7
4.2 Using this Manual ......................................................................................... 7
4.3 Alumina Refining Inputs/Outputs............................................................. 8
5.0 IDENTIFICATION OF INDUSTRY EMISSIONS.......................................... 13
5.1 Combustion Sources ..................................................................................... 13
5.2 Aggregate Handling and Storage ............................................................... 14
5.2.1 Bauxite........................................................................................................ 14
5.2.2 Limestone and Other Aggregate ............................................................ 15
5.3 Bulk Chemical Handling and Storage....................................................... 16
5.4 Bauxite processing......................................................................................... 16
5.4.1 Grinding..................................................................................................... 16
5.4.2 Digestion.................................................................................................... 17
5.4.3 Precipitation and Clarification ............................................................... 18
5.4.4 Classification ............................................................................................. 18
5.5 Drying/Calcining ........................................................................................... 19
5.6 Spent Process Material Storage................................................................... 19
5.7 Maintenance and Support Functions......................................................... 20
6.0 EMISSIONS TO AIR ............................................................................................ 21
6.1 Combustion Sources ..................................................................................... 21
6.1.1 NPI-Listed Substances ............................................................................. 21
6.1.1.1 SO2 Emissions Using Mass Balance............................................................... 22
6.1.1.2 Emissions of NPI-Listed Substances Using Emission Factors.................... 22
6.1.2 Organic Compound Emissions............................................................... 25
6.1.3 Trace Elements from Combustion Sources........................................... 25
6.1.3.1 Mass Balance ..................................................................................................... 26
6.1.3.2 Emission Factors ............................................................................................... 26
6.2 Emissions from Materials Handling and Storage ................................... 28
6.3 Process Sources .............................................................................................. 28
Alumina Refining i
6.3.1 Emission Factors....................................................................................... 28
6.3.2 Control Technologies ............................................................................... 29
6.4 VOC Emissions .............................................................................................. 30
6.4.1 Total VOC Emissions ............................................................................... 30
6.4.2 VOC Speciation......................................................................................... 30
6.4.2.1 Speciation Based on Process Stream Composition ...................................... 30
6.4.2.2 Speciation Using Developed Weight Fraction Data .................................... 31
6.5 Materials Storage ........................................................................................... 32
6.5.1 Acid Storage ....................................................................................................... ..31
6.5.2 Organic Liquids Storage.......................................................................... 32
6.6 Trace Element Speciation............................................................................. 33
7.0 MASS BALANCE .................................................................................................. 34
7.1 Overall Facility Mass Balance ..................................................................... 34
7.2 Individual Unit Process Mass Balance ...................................................... 37
8.0 MONITORING ...................................................................................................... 38
9.0 EMISSIONS TO WATER..................................................................................... 40
10.0 EMISSIONS TO LAND........................................................................................ 44

10.1 Groundwater Monitoring .......................................................................... 44
10.2 Spills............................................................................................................... 45
10.3 On-Site Disposal.......................................................................................... 46
11.0 ASSUMPTIONS AND DISCUSSION .............................................................. 47
Combustion Sources ......................................................................................... 47
Trace Elements................................................................................................... 47
12.0 REFERENCES ......................................................................................................... 48
APPENDIX A: NPI SUBSTANCES RELEVANT TO ALUMINA REFINING ...... 49
APPENDIX B: PROCESS DESCRIPTION AND FLOW DIAGRAM...................... 53
Alumina Refining ii
ALUMINA REFINING
LIST OF FIGURES & TABLES
Figure 1. Raw Materials Handling.......................................................................................9

2. Digestion................................................................................................................10
3. Drying and Calcining..........................................................................................10
4. Liquor Purification ..............................................................................................11
5. Maintenance and Renovation Operations ......................................................12
6. Water Management..............................................................................................12
Table 1. Activities with the Potential to Trigger NPI Reporting ............................. 2

2. NPI Substances Emitted from Combustion................................................ 14
3. NPI Emissions from Bauxite Storage and Handling................................. 15
4. NPI Emissions from Lime/Limestone Storage and Handling................. 15
5. NPI Emissions from Bulk Chemical Storage.............................................. 16
6. NPI Emissions from Grinding of Bauxite .....................................................19
7. NPI Emissions from Digestion...................................................................... 17
8. NPI Emissions from Precipitation and Clarification ................................ 18
9. NPI Emissions from Calcining...................................................................... 19
10. NPI Emissions from Spent Material Processing........................................ 20
11. NPI Emissions from Maintenance and Support Functions ..................... 20
12. NPI-Listed Substances Emission Factors for Fuel Oil Combustion ........26
13. NPI-Listed Substances Emission Factors for Gas Combustion ................27
14. Emission Factors For Organic Emissions from Oil Combustion..............28
15. Emission Factors For Organic Emissions from Gas
Combustion.........................................................................................................29
16. Emission Factors For Trace Elements From Fuel Oil
Combustion.........................................................................................................30
17. Emission Factors For Trace Elements From Gas
Combustion.........................................................................................................31
18. Emission Factors for Alumina Refining Processes.................................... 29
19. Speciation of VOCs for Alumina Refining................................................. 31
20. Acid Properties ................................................................................................. 31
21. Speciation Data from Alumina Refining .................................................... 33
22. Example 2: Measurement Data ........................................................................43
Alumina Refining iii

1.0 Introduction
The purpose of all Emission Estimation Technique (EET) Manuals in this series is to assist
Australian manufacturing, industrial, and service facilities to report emissions of listed
substances to the National Pollutant Inventory (NPI). This Manual describes the
procedures and recommended approaches for estimating emissions from the alumina
refining industry.
EET MANUAL: Alumina Refining
HANDBOOK: Alumina Production
ANZSIC CODE: 2721
The alumina refining activities covered by this Manual include:
• Raw material handling and storage;

• Bauxite processing (including grinding, digesting, precipitating, and drying);
• Ancillary operations including descaling, residue storage, and associated maintenance
activities; and
• On-site combustion.
This Manual was drafted by Pacific Air & Environment, in conjuction with the NSW
Environment Protection Authority, on behalf of the Commonwealth Government.
The Manual has been developed through a process of national consultation involving State
and Territory environmental authorities and key stakeholders. Particular thanks are due
to the Australian Aluminium Council and its members for their comments, advice, and
information.
Alumina Refining 1
2.0 Reportable Substances
The NPI Guide at the front of this Handbook provides guidance to help you determine:
• Whether you are required to report under the NPI; and

• What substances are to be reported.
Section 2 of The NPI Guide details the necessary steps to be taken to assess whether your
facility triggers any thresholds for the substances listed under the NPI. A series of
worksheets are provided to assist with this exercise.
Steps 1 to 4 below provide some general guidance on the substances that are likely to
require reporting.
Step 1: Identify activities that trigger thresholds
Review the activities that have the potential to trigger reporting based on the threshold
criteria in The NPI Guide. Table 1 presents the activities associated with alumina refining
that have the potential to trigger thresholds.
Table 1. Activities with the Potential to Trigger NPI Thresholds. a

Activity Threshold Trigger Category
Combustion (fuel type and usage) b,d Category 2a and 2b substances
Storage/use of bauxite c,d Category 1
e
Storage/use of bulk chemicals Category 1
e
Maintenance and Support Category 1
a
Appendix A of this Manual lists the NPI substances that are expected to be emitted from alumina
refining facilities.
b
Due to the amount of fuel consumed, it is likely that all alumina refineries will be required to report
on the listed Category 2a and 2b substances.
c
The trace metals present in bauxite may lead to reporting thresholds being exceeded. For
example, an alumina refinery handling 500,000 tonnes of bauxite annually would need 20 ppm of an
NPI-listed substance in the bauxite to trigger reporting for that substance.
d
When reviewing each operation, ensure that all feedstock is reviewed for trace metals that may be
present.
e
Material Safety Data Sheets (MSDSs) can be reviewed to determine the composition of other products
used on site.
Step 2: Calculate the quantity of each substance to ascertain if reporting threshold has
been triggered
Using data on the composition of each substance (ie. MSDS, laboratory analysis, or other),
multiply the concentration of each NPI-listed substance present by the annual usage. For
example, if you know the trace metal composition of the bauxite, multiply the
concentration of NPI-listed metals by the total annual tonnage used. This should be done
for each aggregate (and other relevant raw materials) used in the refining process. If the
total quantity of any NPI-listed substance exceeds 10 tonnes, then you must report the
emissions of that substance wherever it is released in the facility.
Alumina Refining 2
Step 3: Identify activities associated with the emission of each NPI substance
Section 5 of this Manual identifies the unit activities that produce (or may produce)
emissions of NPI-listed substances. It is important to recognise that, for each substance,
there may be more than one activity that leads to its emission.
Step 4: Identify appropriate EETs for use in quantifying emissions
Once you have identified each activity that has the potential to release the substances, the
next step is to identify an appropriate EET for the estimation of emissions. EETs for air,
water, and land are provided in Sections 6, 9, and 10 of this Manual respectively. Specific
guidance on the application of mass balance, and monitoring to emissions estimation are
provided in Sections 7 and 8 respectively.
Additional guidance on the interpretation of ‘transfers’ as it applies to alumina refining is

provided in Section 4.
NPI Substances
Category 1 and 1a Substances
The reporting criteria for Category 1 and 1a substances, as detailed in Clause 10 of the NPI
NEPM, are:
• a Category 1 listed substance is only reportable if 10 tonnes or more of the substance is

used per annum;
• the only Category 1a substance is Total Volatile Organic Compounds (VOCs) for which
the throughput threshold is 25 tonnes per annum;
• “use” means processed (eg. crude oil throughput, production chemicals, drilling
fluids), or coincidental production (eg substances contained in produced formation
water, emissions from dehydrator regeneration etc); and
• substances in proprietary mixtures are not reportable unless the substance is specified
in a Material Safety Data Sheet or, in the case of any other material, the occupier of the
facility could reasonably be expected to know that the substance is contained in the
material.
The usage of each of the substances listed as Category 1 and 1a under the NPI must be
estimated to determine whether the 10 tonnes (or 25 tonnes for VOCs) reporting threshold
is exceeded. If the threshold is exceeded, emissions of these Category 1 and 1a substances
must be reported for all operations/processes relating to the facility, even if the actual
emissions of the substances are very low or zero.
The total amount of each Category 1 and 1a substance ‘used’ must be calculated in order
to determine whether the threshold is exceeded. This involves developing a cumulative
total for the use of each NPI substance from various sources.
Alumina Refining 3
3.0 Emission Estimation Techniques
Estimates of emissions of NPI-listed substances to air, water and land should be reported
for each substance that triggers a threshold. The reporting list and detailed information on
thresholds are contained in The NPI Guide at the front of this Handbook.
In general, there are four types of emission estimation techniques (EETs) that may be used
to estimate emissions from your facility.
The four types described in The NPI Guide are:
• sampling or direct measurement;

• mass balance;
• fuel analysis or other engineering calculations; and
• emission factors.
Select the EET, (or mix of EETs), that is most appropriate for your purposes. For example,
you might choose to use a mass balance to best estimate fugitive losses from pumps and
vents, direct measurement for stack and pipe emissions, and emission factors when
estimating losses from storage tanks and stockpiles.
If you estimate your emission by using any of these EETs, your data will be displayed on
the NPI database as being of ‘acceptable reliability’. Similarly, if your relevant
environmental authority has approved the use of EETs that are not outlined in this
handbook, your data will also be displayed as being of ‘acceptable reliability’.
This Manual seeks to provide the most effective emission estimation techniques for the
NPI substances relevant to this industry. However, the absence of an EET for a substance
in this handbook does not necessarily imply that an emission should not be reported to the
NPI. The obligation to report on all relevant emissions remains if reporting thresholds
have been exceeded.
You are able to use emission estimation techniques that are not outlined in this
document. You must, however, seek the consent of your relevant environmental
authority. For example, if your company has developed site-specific emission factors,
you may use these if approved by your relevant environmental authority.
You should note that the EETs presented in this manual relate principally to average
process emissions. Emissions resulting from non-routine events are rarely discussed in
the literature, and there is a general lack of EETs for such events. However, it is important
to recognise that emissions resulting from significant operating excursions and/or
accidental situations (eg. spills) will also need to be estimated. Emissions to land, air and
water from spills must be estimated and added to process emissions when calculating
total emissions for reporting purposes. The emission resulting from a spill is the net
emission, ie. the quantity of the NPI reportable substance spilled, less the quantity
recovered or consumed during clean up operations.
Alumina Refining 4
There is a range of EETs available for the estimation of emissions from alumina refining.
The EETs presented in this Manual as alternatives to direct measurement are:
• emission factors;
• mass balance; and
• software models.
Each of these EETs are discussed briefly in Sections 3.1 to 3.3 below.
3.1 Use of Emission Factors
Emission factors are generally developed through the testing of a particular source
population (eg. various boilers combusting a particular fuel). This information is used to
relate the quantity of a pollutant emitted to some general measure of the activity. For
example, boiler emission factors are typically expressed as emissions per quantity of fuel
consumed. Because emissions estimated using emission factors are not derived through
testing the actual source, they are subject to uncertainty.
Emission factors require ‘activity data’, which is combined with the factor to generate the
emission estimates. The generic formula is:
Ekpy,i = [A * OpHrs] EFi * [1 - (CEi/100)] (1)
where :
Ekpy,i = emission rate of pollutant i, kg/yr

A = activity rate, t/hr
OpHrs= operating hours, hr/yr
EFi = uncontrolled emission factor of pollutant i, kg/t
CEi = overall control efficiency of pollutant i, %.
3
For example, if the emission factor has units of ‘kg pollutant/m of fuel burned’, then the
3
activity data required would be ‘m fuel burned/hr’, thereby generating an emission
estimate of ‘kg pollutant/hr’.
3.2 Mass Balance Techniques
Mass balance involves the quantification of total materials into and out of a process, with
the difference between inputs and outputs being accounted for in terms of emissions to the
environment, or as part of the facility waste. Mass balance is particularly useful when the
input and output streams can be quantified, and this is most often the case for individual
process units and operations.
Mass balance techniques can be applied across individual unit operations, or across an
entire facility. These techniques are best applied to systems with prescribed inputs,
defined internal conditions, and known outputs. It is essential to recognise that the
estimates derived using mass balances are only as good as the values used in performing
the calculations. For example, small errors in data or calculation parameters (eg. pressure,
temperature, stream concentration, flow, control efficiencies etc) can result in large errors
in the final emission estimations. In addition, if sampling of input or output materials is
Alumina Refining 5
conducted, failure to use representative samples will also contribute to the uncertainty of
the result. Section 7 of this Manual provides additional guidance on the application of
mass balance techniques, as well as a worked example.
3.3 Software Models
Software models are available that predict emission rates for fugitive emissions, landfills,
lagoons, open dumps, waste piles, land treatment operations, and other source areas.
These can be used either as a “screening” tool, or for in-depth investigations that require
site-specific data. A range of information (eg. chemical and/or physical characteristics of
specific substances) is typically also required to utilise such software packages. The use of
these software packages has been included in this Manual (where relevant), for the
purpose of characterising and estimating emissions.
While software models frequently require an initial investment of time, they can provide
long term benefits because they can be used relatively easily and quickly to re-estimate
emissions.
Alumina Refining 6
4.0 Locating EETs in this Manual
4.1 Assessing Emissions from your Facility
In this Manual, Emission Estimation Techniques (EETs) are presented in the following
sections:
• Section 6: Emissions to Air;

• Section 9: Emissions to Water; and
• Section 10: Emissions to Land.
Section 6 (emissions to air) is subdivided into defined activities within refining operations,
and where possible, EETs have been identified. However, you should note that there are
substances for which emission estimation techniques are not currently available. In some
cases, it may be possible to use mass balance or available emissions monitoring data to
characterise emissions. You should refer to Sections 7 and 8 of this Manual for additional
guidance on the application of these EETs. If you are unable to estimate emissions using
these EETs, you will need to develop your own EET and have it approved by your State or
Territory Environmental Authority.
Section 9 provides an overview of those emissions to water that are to be reported to the
NPI.
In a similar manner, Section 10 provides some general guidance on those emissions to land
that are reportable to the NPI.
It is important to remember that the Measure for the NPI defines an emission as an
emission of a substance to the environment whether in pure form, or contained in other
matter, and whether in solid, liquid, or gaseous form. It includes the emission of a
substance to the environment from landfill, sewage treatment plants, and tailings dams,
but does not include:
(a) deposit of a substance into landfill; or

(b) discharge of a substance to a sewer or a tailings dam; or
(c) removal of a substance from a facility for destruction, treatment, recycling,
reprocessing, recovery, or purification.
4.2 Using this Manual
The NPI Guide at the front of this Handbook lists all of the substances reportable under the
NPI and the associated reporting thresholds. The NPI Guide should be consulted to
ascertain whether your facility handles, manufactures, or otherwise uses any of the
substances presented in the list, and to determine whether any thresholds are exceeded. If
the facility is found to trigger any thresholds, then emissions to air, water, and land must
be quantified. Once the reportable substances have been identified, the next step is to
establish the substances that are emitted from each activity. Section 5 highlights the NPI
substances potentially emitted from each activity, and indicates whether the emission is to
air, water and/or land. It should be noted that reporting is not required for transfers.
Alumina Refining 7
Once you have reviewed your operations and listed the substances emitted from each
activity, turn to the appropriate section (ie Section 6 for emissions to air, Section 9 for
emissions to water and Section 10 for emissions to land) and apply the EETs as described.
(NB. Note: The information provided in this Manual is comprehensive. However, there are cases
where no EETs are currently available.)
Example 1
For example, Chromium (III) and compounds are NPI-listed substances and
reporting is triggered through fuel use (‘Category 2b’) and compositional make up
of bauxite (‘Category 1’). To quantify emissions of chromium (III) and compounds,
you need to perform the following steps:
Step 1: Identify the activities on site with the potential to emit chromium
The following activities are associated with the emission of chromium (III):
• Combustion (air and, if using coal, also ground and groundwater through
presence of leachate from the ash storage);
• Bauxite handling and storage;
• Bauxite processing; and
• Spent material processing
Step 2: Locate the EETs
EETs for each of the above sources are presented in the following sections:
Air Emissions: Section 6
Section 6.1: Combustion (Section 6.1.3 deals with trace metals);

Section 6.2: Emissions from aggregate handling and storage;
Sections 6.3 and 6.4: Emissions from bauxite processing;
Water Emissions: Section 9
Bauxite storage has the potential for generation of diffuse runoff.

Spent processing material also has the potential to generate runoff.
Land Emissions: Section 10
Leachate from the storage of red mud and ash (if coal is used).
4.3 Alumina Refining Inputs/Outputs
Figures 1 to 6 below show the raw materials inputs to, and outputs from, the various
alumina refining processes expected to result in the emission of NPI-listed substances.
Alumina Refining 8
FIGURE 1: RAW MATERIALS HANDLING
PROCESS
INPUTS OUTPUTS
Unloading AIR
NaOH (impurities include Hg and As) Storage PM10
Acid (sulfuric, hydrochloric) Transfer via rail and Metals
Fuels (natural gas, fuel oil, coal) shipping Acid fume
Bauxite
Limestone (quicklime)
Proprietary chemicals WATER
Solids from bauxite,
limestone in H2O
Alumina Refining 9
FIGURE 2: DIGESTION
PROCESS
INPUTS OUTPUTS
Digestion of
Ground Bauxite AIR
ground bauxite in
NaOH VOCs
hot NaOH
Steam Speciated organics
Re-concentrated spent liquor
from precipitation
FIGURE 3: DRYING AND CALCINING
PROCESS
INPUTS OUTPUTS
Formation of dried AIR

Fuels (natural gas, heavy fuel oil) Al(OH)3 or Al2O3 PM10
Al(OH)3 Transfer of material via Metals (As, Be, Cd, Cr(III,VI),Co, Cu, Pb, Mg, Mn, Hg, Ni, Se, Zn)
rail, conveyor, and CO
shipping NOx
SO2
VOC
Alumina Refining 10
FIGURE 4: LIQUOR PURIFICATION
PROCESS
INPUTS OUTPUTS
Thermal destruction:
Fuel burning of spent liquor AIR
Spent Liquor stream and oxalate PM10
removal (note that other CO
forms of oxalate removal NOx
include biodegredation) SO2
VOC
Alumina Refining 11
FIGURE 5: MAINTENANCE AND RENOVATION OPERATIONS
PROCESS
INPUTS OUTPUTS
Storage
Refractory chemicals AIR
Use
Insulation materials VOCs
Solvents Speciated organics
Cleaning products
Al(OH)3 SOLIDS
Buried Residue
FIGURE 6: WATER MANAGEMENT
PROCESS
INPUTS OUTPUTS
Seawater Water Use and Treatment WATER

Freshwater Wastewater Effluent
Water treatment chemicals
Alumina Refining 12
5.0 Identification of Industry Emissions
This section identifies the basic generic sources that may be relevant to your facility. A
detailed process description and flow diagram are included in Appendix B.
The NPI-listed substances emitted (or expected to be emitted) from the various activities
associated with alumina refining are found in the following sections:
Section 5.1: Combustion sources

Section 5.2: Aggregate storage and handling
Section 5.3: Bulk chemical handling and storage
Section 5.4: Bauxite processing
Section 5.5: Drying/Calcining
Section 5.6: Spent material storage
Section 5.7: Maintenance and support functions
5.1 Combustion Sources
Many facilities generate heat (for further use in the process), energy and/or steam on-site
through combustion of natural gas, fuel oil, and/or coal. Air emissions are the key
emissions from combustion of natural gas and fuel oil. Coal also gives rise to air emissions,
as well as coal ash from the combustion process. Emissions of NPI substances to air from
combustion sources are likely to include the various compounds listed in Table 2.
Alumina Refining 13
Table 2. NPI Substances Emitted from Combustion
NPI Substances Potentially Emitted Emissions to Air Land Emissions
Oxides of Nitrogen EETs for oil and Potential for leachate
SO2 gas are presented from ash storage (See
CO in Section 6 of this Section 10 of this
VOCs including but not limited to: Manual. Manual).
Benzene
toluene EETs for coal
xylenes combustion
ethylbenzene presented in
PAHs Emission Estimation
formaldehyde Technique Manuals
for Combustion in
acetone
Boilers and Fossil
n-hexane
Fuel Electric Power
acetaldehyde
Generation.
phenol
PM10 giving rise to the following
speciated substances:
antimony and compounds
arsenic and compounds
beryllium and compounds
cadmium and compounds
chromium (III) compounds
chromium (VI) compounds
cobalt and compounds
copper and compounds
lead and compounds
fluoride compounds
manganese and compounds
nickel and compounds
selenium and compounds
zinc and compounds
mercury and compounds (fume)
5.2 Aggregate Handling and Storage
5.2.1 Bauxite
Bauxite is transferred from the carrier (in some cases this may be a marine vessel), or
directly from the bauxite mine to the site storage via conveyor. The material is stockpiled
on site and transferred to the bauxite processing area for conversion into alumina. Each
facility may have a different set up. A typical bauxite handling and storage scenario
would include the following:
• Unloading or “transporting to processing site” via conveyer;

• Stockpiling; and
• Transfer from stockpile to bauxite processing.
Alumina Refining 14
Potential emissions are provided in Table 3.
Table 3. NPI Emissions from Bauxite Storage and Handling

NPI Substances Potentially Emitted Emissions to Air Water Emissions
PM10 giving rise to the following Fugitive dust (EETs in Potential for diffuse
speciated substances: Section 6) runoff due to rain (EET
arsenic and compounds in Section 7).
boron and compounds
chromium (III) compounds
chromium (VI) compounds
cobalt and compounds
copper and compounds
fluoride compounds
manganese and compounds
selenium and compounds
zinc and compounds
5.2.2 Limestone and other Aggregate
Lime or limestone is transferred on-site and stockpiled. A typical scenario would include
the following:
• Unloading;
• Stockpiling; and
• Transfer to bauxite processing
Potential emissions of NPI substances are provided in Table 4.
Table 4. NPI Emissions from Lime/Limestone Storage and Handling

NPI Substances Emissions to Air Emissions to Water
Potentially Emitted
PM10 Fugitive dust (EETs in Potential for diffuse runoff due to rain
Section 6) (EET in Section 7)
Alumina Refining 15
5.3 Bulk Chemical Handling and Storage
Bulk chemicals stored on site in tanks for use in the process may include:
• hydrochloric acid;
• sulfuric acid;
• diesel;
• petrol;
• LPG;
• chlorine;
• biocides;
• flocculants; and
• defoamers
Note: Other Category 1 substances may also be used in quantities that may trigger the 10
tonne reporting threshold. These will need to be identified and assessed on a facility by
facility basis.
As indicated in Table 5, these substances may be released to air. However, there is also the
potential for emissions to land from spills.
Table 5. NPI Emissions from Bulk Chemical Storage

NPI Substances Potentially Emitted Emissions to Air Emissions to Land
Hydrochloric acid; Storage of these Section 10 provides a
Sulfuric acid; substances in fixed roof discussion on spills, and
VOCs and speciated organics released tanks may give rise to how these may be
from the handling/storage of fugitive emissions into characterised
hydrocarbons the atmosphere (EETs in
Section 6)
5.4 Bauxite processing
Bauxite processing includes grinding, digestion, drying, and calcining. These processes
give rise to air emissions, and the formation of spent process material.
5.4.1 Grinding
The bauxite is crushed and finely ground in a mill prior to the digestion process. The
grinding process gives rise to air emissions as indicated in Table 6. The use of a control
technology, such as a spray tower, floating bed scrubber, or cyclone, can help reduce
particulate emissions. Where grinding is carried out using wet milling, no dust emissions
would be expected.
Alumina Refining 16
Table 6. NPI Emissions from Grinding of Bauxite
NPI Substances Potentially Emitted Emissions to Air
Particulate (including PM10) giving rise to the following speciated Air emissions through
substances: mill ventilation (EETs in
arsenic and compounds; Section 6).
boron and compounds;
chromium (III) compounds;
chromium (VI) compounds;
cobalt and compounds;
copper and compounds;
fluoride compounds;
manganese and compounds;
selenium and compounds; and
zinc and compounds.
5.4.2 Digestion
Finely ground bauxite is slurried with sodium hydroxide solution and lime and reacted at
high pressure and temperature to remove the iron oxides, and most of the silicon oxides.
The pressure, temperature, and retention time in the digester is a function of the mineral
composition of the bauxite. Sodium aluminate is formed, and the silicon, iron, titanium,
and calcium oxides form the insoluble components of the solid waste residual.
During the digestion process, volatile organic components of the ore are vented and
emitted to air as fugitives. Table 7 provides a list of possible NPI substances emitted from
the digestion process.
Table 7. NPI Emissions from Digestion

VOCs including, but not limited to: Fugitive emissions of
Methanol; organic volatiles and
Ethanol; other compounds (EETs
Acetaldehyde; in Section 6).
Acetone;
Benzene;
Cyclohexane;
Ethylbenzene;
Xylenes (all isomers);
Styrene;
Chloroform;
Trichloroethane; and
PAHs.
Other compounds, including:
Hydrogen Sulfide;
Carbon Disulfide; and
Sulfur Dioxide.
Alumina Refining 17
5.4.3 Precipitation and Clarification
The hot slurry is usually cooled by flash evaporation, producing steam that is used to
preheat the incoming slurry. The slurry is then processed in a series of clarification steps
designed to separate the solid residual from the liquor. The steps can include the
following:
• Passage of slurry through hydrocyclones to remove grit;

• Addition of flocculant (ie. starch or other settling agents) to settle fine particles;
• Filtration of clear overflow;
• Washing of underflow in thickeners to remove caustic, which is then sent on as spent
product;
• Sending of filtrate (containing sodium aluminate) to precipitator; and
• Crystallisation and precipitation of aluminum hydroxide.
As indicated in Table 8, the precipitator may also give rise to fugitive emissions of volatile
organic substances similar to the substances identified for the digester.
Table 8. NPI Emissions from Precipitation and Clarification

VOCs including, but not limited to: Organic volatiles and
Methanol; other compounds
Ethanol; released through
Acetaldehyde; process vents
Acetone; (EETs in Section 6).
Benzene;
Cyclohexane;
Ethylbenzene;
Xylenes (all isomers);
Styrene;
Chloroform;
Trichloroethane; and
PAHs.
Other compounds including:
Hydrogen sulfide;
Carbon disulfide; and
Sulfur dioxide.
5.4.4 Classification
After precipitation, the slurry (containing trihydrate crystals) is sent to classification where
the product is classified according to crystal size. The coarse particles are:
• washed to remove excess sodium hydroxide;

• dewatered on vacuum filters; and
• sent to calcination.
The finer crystals are recycled to the precipitation process as seed, thereby providing
nucleation sites for precipitation to occur. Spent liquor from the precipitators is recycled
to the digesters.
Alumina Refining 18
5.5 Drying/Calcining
The coarse alumina is calcined in rotary kilns or fluid-bed calciners at about 1000°C.
During calcination, water is driven off. Calciners produce hot flue gases containing
alumina and water vapour. Two types of kilns are used in the refining industry: oxalate,
and liquor burning. CO is produced in the oxalate process.
Typical control equipment includes cyclonic separators, followed by ESPs. The control
equipment can also be used to recover product as well as to minimise emissions. Typical
emissions are provided in Table 9. You should note that the emissions associated with this
activity depend on the specific fuel being used.
Table 9. NPI Emissions from Calcining

VOCs Stack emissions from
PAHs the kiln (EETs in
CO Section 6).
NOX
SO2
PM10 giving rise to the following speciated substances:
arsenic and compounds;
boron and compounds;
chromium (III) compounds;
chromium (VI) compounds;
cobalt and compounds;
copper and compounds;
fluoride compounds;
zinc and compounds.
5.6 Spent Process Material Storage
The following spent process material is generated during the refining process:
• red mud from precipitator and clarifier;

• refractory linings (linings from furnaces, and reactors, etc);
• descaling waste (scrapping out vessel); and
• coal ash from coal combustion.
Since these materials are processed on-site, they do not need to be reported under the NPI.
The potential for emission of NPI substances occurs under the following circumstances:
• leachate is emitted into the ground and/or groundwater; and/or

• runoff from the site is emitted into a water body; and/or
• fugitive air emissions are emitted into the atmosphere.
An indication of the possible NPI emissions and associated sources are provided in Table
10.
Alumina Refining 19
Table 10. NPI Emissions from Spent Material Processing
NPI Substances Potentially Source Emissions Emissions Emissions
Emitted to Air to Water to Land
PM10 giving rise to the following Red mud Fugitive Surface Leachate
speciated substances: from emissions runoff (EETs in
arsenic and compounds; alumina from the (EETs in Section 10)
boron and compounds; processing surface Section 9)
chromium (III) compounds; (storage)
chromium (VI) compounds; as well as
cobalt and compounds; handling
copper and compounds; (EETs in
Section 6)
fluoride compounds;
zinc and compounds.
Organics (see precipitation)
Chromium (III) and Refractory Refractory Refractory Refractory
Chromium (VI) compounds waste waste waste waste
See above (red mud) Descaling Descaling Descaling Descaling
waste waste waste waste
Organics Coal ash Coal ash Coal ash Coal ash
Metals as per red mud
5.7 Maintenance and Support Functions
Maintenance and support functions are unlikely to trigger the reporting of NPI substances
because of the quantities of materials handled. However, a substance may be reportable as
a result of other activities that do trip thresholds and hence, maintenance and support
emissions will need to be included as indicated in Table 11.
Table 11. NPI Emissions from Maintenance and Support Functions

NPI Substances Potentially Emitted Source Emissions to Air
See Appendix A for listing of Solvent usage for EET in Section 6
potential solvents maintenance
Alumina Refining 20
6.0 Emissions to Air
Emissions to the atmosphere are divided into the following generic categories:
• Section 6.1: Combustion sources (ie. furnaces and boilers);

• Section 6.2: Materials handling and storage;
• Section 6.3: Process emissions (eg. precipitation, digestion etc.); and
• Section 6.6: Vent emissions from bulk storage.
Sections 6.4 and 6.5 respectively, provide guidance on the speciation of emissions of
particulate matter, and VOCs. In addition to the EETs discussed in this Section, the
general application of mass balance techniques and monitoring for emission estimations
are discussed in Section 7 and Section 8 of this Manual.
6.1 Combustion Sources
Combustion is a process used in alumina refining. Natural gas and fuel oil combustion
emissions are considered in this section.
NB: Air emissions from coal combustion are handled separately in the ‘Emission Estimation
Technique Manual for Combustion in Boilers’ and the ‘Emission Estimation Technique Manual for
Fossil Fuel Electric Power Generation’.
For the purposes of this Manual, the NPI substances emitted from combustion processes
are divided as follows:
• Section 6.1.1: NPI-Listed Substances (NOx, SO2, PM10, CO and total VOCs);
• Section 6.1.2: Organic compound speciation; and
• Section 6.1.3: Trace elements from Combustion Sources (including metals and
compounds such as fluorides, ammonia, carbon disulfide, etc.).
Holding furnaces are also included in the ‘combustion category’.
6.1.1 NPI-Listed Substances
The NPI-listed substances released by combustion sources are:
• Oxides of nitrogen (NOx);

• Sulfur dioxide (SO2);
• Particulate matter less than 10 micrometres (PM10);
• Carbon monoxide (CO); and
• Volatile organic compounds (VOCs).
Emission factors are provided for the estimation of these pollutants with the exception of
SO2, for which the preferred estimation technique is mass balance based on the sulfur
content of the fuel.
Alumina Refining 21
6.1.1.1 Emissions of SO2 Using Mass Balance
Estimates of SO2 emissions can be made using the following equation, which assumes
100% conversion of sulfur to SO2:
Emission of SO2 (kg/hr) = Fuel Usage (kg/hr) * (wt%S/100) * 2 (2)
Where:
Fuel Usage = the feed rate of fuel (ie. oil or gas) to the combustion system in
kg/hr
wt%S = the weight percent of sulfur (as elemental S) in the fuel
6.1.1.2 Emissions of NPI-Listed Substances Using Emission Factors
Table 12 and Table 13 below provide emission factors for use in estimating emissions of
the NPI-listed substances from oil, and gas combustion sources respectively. The general
term ‘boiler’ is used in these tables, however, the emission factors also apply to furnaces.
In addition, the term ‘uncontrolled’ indicates that the emission factors assume that no
pollution control devices are used to reduce the respective pollutants (eg. baghouse or ESP
for PM10, Low NOx Burners for NOx reduction, etc).
Alumina Refining 22
Table 12. NPI-Listed Substances Emission Factors for Fuel Oil Combustion a, b
Oil Type and Firing Emission Factors (kg/m3 oil fired)
Configuration
NOx c CO PM10 d VOC
Boilers > 30 MW
No. 6 oil fired, normal firing 5.6 0.6 0.71A+1.5 0.091
e
No. 6 oil fired, normal firing, LNB 4.8 0.6 0.71A+1.5 ND
No. 6 oil fired, tangential firing 3.8 0.6 0.71A+1.5 0.091
No. 6 oil fired, tangential firing, LNB e 3.1 0.6 0.71A+1.5 ND
No.2 oil fired 2.9 0.6 1.54 ND
No.2 oil fired, LNB/FGR e 1.2 0.6 1.54 ND
Boilers < 30 MW
No. 6 oil fired 6.6 0.6 0.86A+1.5 0.034
No. 5 oil fired 6.6 0.6 0.86A+1.5 0.034
No. 4 oil fired 2.4 0.6 0.86A+1.5 0.024
Distillate oil fired 2.4 0.6 1.54 0.024
a
Source: USEPA (1998a). The oil type categories are defined as follows:
No. 5 and 6 Fuel Oil: These are very heavy fuel oils containing significant quantities of nitrogen, sulfur,
and ash. No. 6 fuel oil is sometimes referred to as Bunker C.
No. 4 Fuel Oil: This is typically a mixture of distillate and residual oils.
Distillate Oil: This is more volatile and less viscous than the other oils, has negligible nitrogen and ash
contents, and usually contains less than 0.3 percent sulfur.
b
These emission factors apply to uncontrolled sources, unless otherwise indicated.
c
NOx emission factors are expressed as NO2. A more accurate method for estimating NOx emissions from
industrial boilers (i.e. < 30 MW) is to apply the following equation:
3
kg NO2 /m oil fired = 2.47 + 12.53(N), where N is the weight percent of nitrogen in the oil.
d
Particulate emission factors for residual oil combustion without emission controls are typically a function of
fuel oil grade, and sulfur content:
3
No. 6 oil: A = 1.12(S) + 0.37 kg/m , where S is the weight percent of sulfur in the oil.
3
No. 5 oil: A = 1.2 kg/m
3
No. 4 oil: A = 0.84 kg/m
Depending on the fuel type burned, the appropriate factor for ‘A’ should be substituted where known into
the relevant PM10 factor in the table.
e
LNB = Low NOX Burners, FGR = Flue Gas Recirculation
Alumina Refining 23
Table 13. NPI-Listed Substances Emission Factors for Gas Combustion a
Combustion System Type Emission Factors (kg/106 m3 gas fired)
b
NOx CO PM-10 VOC
Wall Fired Boilers > 30 MW
Uncontrolled 4480 1344 122 88
Controlled – Low NOx burners 2240 1344 122 88
Controlled – Flue gas recirculation 1600 1344 122 88
Boilers < 30 MW
Controlled – Low NOx burners 800 1344 122 88
Tangential-Fired (All Sizes)
a
Source: USEPA (1998b). These emission factors are based on the fuel gas at 15 degrees C and 1 atm.
b
NOx emission factors are expressed as NO2.
Scaling Emissions According to Heating Value
The emission factors presented in Table 12 and Table 13 are based on the volumetric
quantity of fuels burned in each boiler/furnace. These factors are based on fuels with the
standard heating values listed below:
• Fuel oil No. 4, 5 and 6: 41.8 GJ/m3

• Fuel oil No. 2 and distillate: 39 GJ/m3
• Fuel gas: 37.2 MJ/m3
While it is stated in AP-42 (USEPA, 1997a) that the gas heating value is the higher heating
value, no information of this nature is specified with regards to the oil heating values.
However, as the gas data refers to the higher heating value, it is assumed that this also
applies to the oil heating values.
Emissions calculated using the emission factors provided in Table 12 and Table 13 must
be scaled according to a ratio of the fuel’s actual heating value, to the standard values
supplied above. The emission factors provided in the tables should be applied using the
following generic formula:
Ei = EFi * Qf * Actual Heating Value/Standard Heating Value (3)
Ei = Emission, kg/hr
EFi = Emission factor, kg/m3
3
Qf = Fuel usage, m /hr
Alumina Refining 24
6.1.2 Organic Compound Emissions
There are a range of organic compounds released during the combustion of fuel oil and
gas. For those organic compounds on the NPI substance list, emission factors are
presented in Table 14 and Table 15 for oil, and gas combustion respectively.
It is important to note that the emission factors presented in Table14 and Table 15 reflect
the data available in the literature. It is possible that other NPI substances are also
emitted, but no information on such emissions is available. Refer to Section 11.0 for a
discussion of these emission factors.
Table 14. Emission Factors for Organic Emissions from Oil Combustion a
NPI Substance Emission Factor (kg/106 m3 oil fired)
Benzene 2.57 * 10-5
Toluene 7.44 * 10-4
Xylenes b 9.01 * 10-4
-6
Ethylbenzene 7.63 * 10
PAH’s 1.43 * 10-4
Formaldehyde 3.96 * 10-3
c -2
Acetone 1.01 * 10
n-Hexane c 1.80 * 10-3.
a
Source: USEPA (1998a), unless otherwise indicated.
b
Source: USEPA (1997b).
c
Source: USEPA (1993).
Table 15. Emission Factors for Organic Emissions from Gas Combustion a
6 3
Organic Compound Emission Factor (kg/10 m gas fired)
-2
Benzene 3.4 * 10
Toluene 5.4 * 10-2
Acetaldehyde b 0.13
Formaldehyde 1.2
Phenol b 0.062
PAH’s 1.1 * 10-2
n-Hexane 29
a
Source: USEPA (1998b), unless otherwise indicated.
b
Source: USEPA (1997b).
You should note that, in a similar manner to the estimation of emissions of NPI-listed
substances resulting from the combustion of oil and gas, the emissions calculated using
the emission factors provided in Table 14 and Table 15 must be scaled, based on the
fuel’s actual heating value. (See Section 6.1.1.2 for a further discussion of this).
6.1.3 Trace Elements from Combustion Sources
Emissions of certain trace elements can be estimated using mass balance when fuel
composition data is available. If such data is unavailable, default emission factors can be
used. This Section is divided into two categories, with the first examining emission
estimation using mass balance (ie. where and how it is applicable), and the second relating
to emission factors.
Alumina Refining 25
6.1.3.1 Mass Balance
Mass balance is the preferred methodology for estimating ‘uncontrolled’ emissions of

metals resulting from fuel and gas combustion. This approach assumes that 100 percent of
the trace elements present in the fuels are released into the atmosphere upon combustion
(this assumption is discussed further in Section 11.1.2).
To use this mass balance methodology, the two key data requirements are:
1. The metal content of the fuels utilised in each boiler and furnace; and
2. The fuel consumption rate for each combustion source.
The above inputs can then be applied using the following equation:
ER = Qf * Metal Content of Fuel (wt%)/100 (4)
ER = Emission rate, kg/hr

Qf = Fuel usage, kg/hr
Example 2
The following data is known about the fuel and its usage at a refinery:
• the cadmium (Cd) content of the fuel oil is approximately 0.3 ppmwt (parts per
million by weight); and
• the fuel oil usage of the boiler is approximately 1100 kg/hr.
Therefore, the emission rate of ‘cadmium and compounds’ (assuming that

100 percent of the cadmium entering the boiler is released in the flue gases) is
derived as follows:
1100 kg/hr fuel oil * 0.3 kg Cd/106 kg fuel oil = 3.3 * 10-4 kg/hr
The uncontrolled emission rate of cadmium and compounds is, therefore, 3.3 * 10-4
kg/hr.
6.1.3.2 Emission Factors
In the event that insufficient data is available to derive emission estimates of metals using
mass balance, the emission factors presented in Table 16 and Table 17 may be used for oil
and gas combustion respectively. The oil types relating to Table 16 are discussed in
Section 6.1.1.2. The general use of emission factors is discussed in Section 3.1.
Alumina Refining 26
Table 16. Emission Factors for Trace Elements from Fuel Oil Combustion a
Trace Element (and Distillate Oil Combustion b Residual Oil Combustion c
Compounds) (kg/m3) (kg/m3)
Antimony ND d 6.3 * 10-4
Arsenic 6.71 * 10-5 1.5 * 10-4
-5 -6
Beryllium 5.03 * 10 3.3 * 10
Cadmium 5.03 * 10-5 4.8 * 10-5
Chromium (III) e ND 7.2 * 10-5
Chromium (VI) ND 3.0 * 10-5
Cobalt ND 7.2 * 10-4
-4
Copper 1.01 * 10-4 2.1 * 10
Lead 1.51 * 10-4 1.8 * 10-4
Manganese 1.01 * 10-4 3.6 * 10-4
Mercury 5.03 * 10-5 1.4 * 10-5
Nickel 5.03 * 10-5 1.0 * 10-2
-5
Selenium 2.52 * 10-4 8.2 * 10
Zinc 6.67 * 10-5 3.5 * 10-3
Fluoride ND 4.5 * 10-3
a
Source: USEPA (1997a).
b
‘Distillate’ also includes No. 2 fuel oil (refer to Section 6.1.1.2).
c
‘Residual’ includes fuel oil No. 4, 5 and 6 (refer to Section 6.1.1.2).
d
‘ND’ = No data available.
e
Data was supplied for total Cr and Cr(VI). The estimate for Cr(III) was derived by assuming that
after subtracting Cr(VI), all remaining Cr is trivalent (ie. Cr(III).
Table 17. Emission Factors for Trace Elements from Gas Combustion a
Trace Element (and Compounds) Emission Factor (kg/106 m3)
Arsenic 3.2 * 10-3
Beryllium 1.9 * 10-4
b -3
Chromium (VI) 1.1 * 10
Cobalt 1.3 * 10-3
Copper 1.4 * 10-2
Cadmium 1.8 * 10-2
Lead 8.0 * 10-3
Manganese 6.1 * 10-3
Mercury 4.2 * 10-3
Nickel 3.4 * 10-2
Selenium 3.8 * 10-4
Zinc 4.6 * 10-1
a
Source: USEPA (1998a) unless otherwise indicated.
b
Source: USEPA (1997b)
You should note that reporting is only required for those substances that trigger reporting
thresholds. It is possible that these thresholds are not triggered for all of the compounds
listed in the tables above. Refer to The NPI Guide at the front of this Handbook for more
information.
Alumina Refining 27
6.2 Emissions from Materials Handling and Storage
In the specific context of alumina refining, no EETs are currently available to quantify
emissions from these operations. However, many of the materials handling and storage
activities conducted at alumina refineries are similar to those found at mine sites (see the
Emission Estimation Technique Manual for Mining for further details).
6.3 Process Sources
Emission estimation techniques for grinding, precipitation, digestion, drying and calcining
will vary depending on the type of data available. The intent of the NEPM and the
Memorandum of Understanding is that no additional monitoring of emissions will be
required over and above that already conducted by facilities (eg. for licensing, and/or
other regulatory requirements). If source testing is performed for other compliance
programs, then the results can be used for emissions estimation.
You should note that in addition to the EETs discussed in this Section, emissions can be
estimated using other methodologies provided in this Manual such as mass balance (refer
Section 7) and/or monitoring data (refer Section 8).
6.3.1 Emission Factors
An alternative to direct measurement or mass balances is the use of emission factors. You
should note that although the number of NPI-listed substances presented in this Section is
limited, other NPI-listed compounds may also emitted.
Emission factors for particulate and fluoride emissions from grinding and calcining
operations are presented in Table 18. In addition, you should refer to Section 6.4 of this
Manual for additional guidance regarding the speciation of particulate emissions.
There is limited information available on emissions of volatile organic compounds (VOCs)

from process operations. Section 6.6 of this Manual discusses VOC emissions further, and
provides additional information regarding the speciation of VOC emissions.
Alumina Refining 28
Table 18. Emission Factors for Alumina Refining Processes a
Operation Total Particulate d,e(kg/tonne)
Bauxite grinding b
Uncontrolled 3
Spray tower 0.9
Floating bed scrubber 0.85
Quench tower and spray screen 0.5
Aluminum hydroxide calcining
c
Uncontrolled 100
Spray tower 30
Floating bed scrubber 28
Quench tower 17
ESP 2
a
Source: USEPA, (1997a). For bauxite grinding, factors expressed as kg/tonne bauxite
processed. For aluminium calcining, factors expressed as kg/tonne of alumina produced.
Neg = negligible
b
Note that many Australian alumina refineries use wet milling. In this situation, the dust
emissions are expected to be zero.
c
After multicyclones
d
The data available in the literature pertains to total particulate rather than the NPI-listed
PM10. In the absence of better data, the total particulate data can be used to provide
conservative upper bounds for PM10 emissions.
e.
With regards to emission controls for PM10, in the absence of measured data, or knowledge of the
collection efficiency for a particular piece of equipment, an efficiency of 90% should be used in the emission
factor equation to calculate actual mass emissions. This default should only be used if there is no other
available control efficiency.
6.3.2 Control Technologies
As shown in Table 18 above, emission factors are available for both uncontrolled and
controlled emissions.
Where available however, it is preferable to use the actual pollutant reduction efficiencies
of control technologies, rather than the defaults provided above. ‘Actual’ control
efficiency data can be combined with an ‘uncontrolled’ emission estimate using Equation
1, an example is presented below.
This equation can be applied when uncontrolled emissions and the control efficiency
associated with the particular control equipment utilised are known.
Alumina Refining 29
Example 3
The ‘uncontrolled’ emission estimate for PM10 from calcining is 5000 tonnes
per year. A wet scrubber, with a known reduction efficiency of 90 percent, is
used to aid in controlling emissions. Therefore, using Equation 1, the
‘controlled’ emission estimate is derived as follows:
Controlled Emission = 5000 * (1-90/100)

= 5000 * 0.1
= 500 tonnes/annum
Thus, the particulate emission after considering the particulate emission

control is 500tonnes/annum.
6.4 VOC Emissions
6.4.1 Total VOC Emissions
Very little data is available to estimate total VOC emissions from alumina refining
operations. Currently, emissions can only be estimated using source test data collected at
refining facilities, if such data is available. Total VOC emission estimates can then be
speciated using the methodologies outlined in the following section.
6.4.2 VOC Speciation
Once total VOC emissions have been estimated, these emissions can be speciated into NPI-
listed substances using either:
1. Process stream composition data; and/or

2. Available speciation data (in the form of weight fractions) from the USEPA.
The first methodology is likely to give more accurate estimates than those derived by
using generic weight fractions developed by the USEPA. The speciation data from USEPA
is limited and, therefore, a combination of these two methodologies may be required.
Each of these VOC speciation methods will be discussed in greater detail in the following
sections.
6.4.2.1 Speciation Based on Process Stream Composition
This methodology involves using the compositional data for each process stream (ie.
obtained from analytical procedure such as GC/MS), and applying this data to
approximate the vapour phase composition.
Alumina Refining 30
This EET relies on the following equation to speciate emissions from a single source:
EI= EVOC * (WPi / WPVOC) (5)
Where:
Ei = The mass emissions of NPI substance "i" (kg/hr)

EVOC = The total VOC mass emission rate from a source (fugitive or
stack)
WPi = The concentration of NPI substance “i” in weight percent
WPVOC = The VOC concentration in weight percent.
6.4.2.2 Speciation Using Developed Weight Fraction Data
In the absence of analytical data, the default VOC speciation data presented in Table 19
can be used to characterise emissions of NPI-listed substances. As previously mentioned,
only limited VOC speciation data has been found in the literature. Applying this
speciation data requires the use of an equation similar to that in Section 6.4.2.1, as follows:
Ei = EVOC * (WPi / 100) (6)
Where:
Ei = The mass emissions of NPI substance “i” from the source (kg/hr)
EVOC = The total VOC mass emission rate (kg/hr)
WPi = The weight percent of the relevant compound in the VOC emission
(as provided in Table 19).
Table 19. Speciation of VOCs for Alumina Refining a

Substance M Wt Weight Percent
Cyclohexane 84.16 2.3
Formaldehyde 30.03 18.2
Benzene 78.11 9.1
Toluene 92.13 4.5
a
Source: USEPA (1990).
A much greater range of compounds was originally supplied, with the weight fractions all summing to 100%. The compounds shown
in the table above are those present on the NPI substance list.
The degree of speciation that can be performed using this method is limited, and it is
possible that other compounds present on the NPI substance list will be identified in the
VOCs emitted.
Alumina Refining 31
6.5 Materials Storage
6.5.1 Acid Storage
Emissions from the storage of acids can be estimated by assuming that the vapour space
within the storage tank is saturated, and at atmospheric pressure. Using the following
table, and assuming ideal gas properties, an estimate can be derived.
Table 20. Acid Properties a

Acid Partial Pressure (kPa) Volume Percent
Sulfuric Acid b 0.277 * 10-5 2.73 * 10-6
c
Hydrochloric Acid 1.41 1.4
a Source: Perry & Green (1997). Based on 1 atm and 20C
b Note that Table 2-14 on page 2-82 of Perry & Green (1997) provides an extensive table specifying the
properties of sulfuric acid at various storage temperatures and solution concentrations. The term
‘Vol%’ above (and in the equation below) is derived by dividing the partial pressure taken from this
table, by the ambient pressure of 101.3 kPa (note that the pressure data as read from the table in
Perry’s is in units of ‘bars’).
c Concentration = 30%. Similarly to footnote b, Table 2-10 on page 2-76 in Perry & Green (1997)
provides relevant hydrochloric acid properties.
To estimate emissions during filling operations to acid storage tanks, the following
formula can be used (based on the ideal gas law):
E = 0.042 * MW * VVS * (Vol%/100) (7)
Where:
E = Mass of acid emitted during filling (kg)

MW = Molecular Weight of acid (for Hydrochloric Acid = 36.5 kg/kmol;
Sulfuric Acid = 98 kg/kmol)
VVS = Volume of the vapor space in the tank = volume of acid added (m3).
Vol% = Volume percent from above table.
6.5.2 Organic Liquids Storage
EETs for the storage of organic liquids (eg. fuels) can be found in the Emission Estimation
Technique Manual for Fuel and Organic Liquid Storage.
Alumina Refining 32
6.6 Trace Element Speciation
Metals can be speciated based on trace analysis data, or MSDS information provided by
the vendor. This data can be combined with particulate emissions data (ie. collected as
source test results and/or calculated by other estimation techniques) using the equation
below:
Ekpy,i = (m)(ci) (8)
Where:
Ekpy,i = mass emission of component i (kg/yr)

m = mass emission rate of particulate (kg/yr)
ci = mass fraction of component i (mg/kg *10-6), see Table 21.
You should note that this methodology is most applicable to emissions from low
temperature sources, such as stockpiles. This is because this methodology is based on the
intrinsic assumption that all metals are contained by the released particulate matter.
While this may be a reasonable assumption for metals with very low vapour pressures,
more volatile metals such as mercury are likely to be partially present in vapour form at
increased temperatures. However, insufficient information is currently available to
produce better estimates than those derived by source testing.
In addition, metals can be speciated in bauxite and red mud using data presented in the
literature, as provided in Table 21. This data can be combined with particulate emission
data using the equation provided above.
a,b,c,d
Table 21. Speciation Data from Alumina Refining
NPI Substance Bauxite (mg/kg) Red Mud (mg/kg)
Antimony 0.2 0.3
Arsenic 16.6 29.0
Beryllium 0.4 0.7
Cadmium 2.6 4.5
Chromium 179.0 314.0
Cobalt 12.6 22.0
Copper 15.4 27.0
Lead 5.7 10.0
Manganese 94.0 165.0
Mercury <0.03 <0.05
Nickel <3.0 <5.0
Selenium <6.0 <10.0
Zinc 18.3 32.0
Boron <12.0 <20.0
Fluorine 645.0 1130.0
a
Source: Department of Agriculture, WA (1993)
b
Based on the ratio 3.5 tonnes bauxite yields 2 tonnes red mud
c
A large Refinery can generate 3.5 Mt/annum
d
WA figures for speciation may not represent all bauxite. It is acknowledged that the mineralogy and
processing efficiencies vary from site to site.
Alumina Refining 33
7.0 Mass Balance
Mass balances involve examining a process to determine whether emissions can be

characterised based on an analysis of operating parameters, material composition, and
total material usage. Mass balance involves the quantification of total materials into and
out of a process with the difference between inputs and outputs being accounted for as an
emission to the environment (to air, water, land), or as part of the facility’s waste. Mass
balance is particularly useful when the input and output streams can be readily
characterised, and this is most often the case for small processes and operations.
Mass balance can be applied across an entire facility or across individual unit operations.
Mass balance techniques and engineering estimates are best used where there is a system
with prescribed inputs, defined internal conditions, and known outputs.
It is essential to recognise that the emission values produced when using mass balance are
only as good as the values used in performing the calculations. For example, small errors
in data or calculation parameters (eg. pressure, temperature, stream concentration, flow,
control efficiencies) can result in potentially large errors in the final estimates. In addition,
when sampling of input and/or output materials is conducted, the failure to use
representative samples will also contribute to uncertainty. In some cases, the combined
uncertainty is quantifiable, and this is useful in determining if the values are suitable for
their intended use.
7.1 Overall Facility Mass Balance
Mass balances can be used to characterise emissions from a facility, providing that
sufficient data is available pertaining to the process and relevant input and output
streams. Mass balances can also be applied to an entire facility (see the example below).
This involves consideration of material inputs to the facility (purchases), and materials
exported from the facility in products and wastes, where the remainder is considered as a
‘loss’ (or an emission to the environment).
Alumina Refining 34
The mass balance calculation can be summarised by:
Total mass into process = Total mass out of process
In the context of the NPI, this equation could be written as:
Inputs = Products + Transfers + Emissions
Where:
Inputs: All incoming material used in the process.

Emissions: Emissions to air, water, and land (as defined under the NPI).
Emissions include both routine and accidental emissions, as well as
spills.
Transfers: As defined under the NPI NEPM, transfers include substances
discharged to sewer, substances deposited into landfill and substances
removed from a facility for destruction, treatment, recycling,
Products: Products and materials exported from the facility.
Applying this to an individual NPI substance (substance ‘i’), the equation may be written
as:
Input of substance ‘i’ = Amount of substance ‘i’ in product + amount of substance ‘i’
in waste + amount of substance ‘i’ transformed/consumed in process + emissions
of substance ‘i’.
The mass balance approach can be used for any NPI-listed substance for which the facility
is required to provide a report. Emissions to air, water and land can then be estimated. A
simple example of the application of mass balance is presented below.
Alumina Refining 35
Example 4
A process uses 10 000 tonnes of raw material A, 5 000 tonnes of raw material B, and
20 000 tonnes of water to produce 22 000 tonnes of product, and 4 000 tonnes of
by-product annually, where A and B are NPI-listed substances (NB. You are required to
quantify NPI-listed substances only). What is the total amount of waste emitted from the
process? How much of this should be reported under the NPI?
The general calculation process is presented as a series of steps:
Step 1: Calculate Total Inputs to Process
Total inputs:
= mass of A + mass of B + mass of water
= 10 000 + 5 000 + 20 000
= 35 000 tonnes
Step 2: Calculate Total Outputs from Process
Total outputs:
= mass of product + mass of by-product
= 22 000 + 4 000
= 26 000 tonnes
Step 3: Calculate Total Amount of Waste Produced
Total quantity of waste produced:

= mass of inputs – mass of outputs
= 35 000 – 26 000
= 9000 tonnes per annum.
Step 4: Identify Transfers and Spills
The facility will need to identify those wastes that are classed as transfers under
the NPI. For example, of the 9000 tonnes per annum of waste produced, 2800
tonnes may be collected and sent for offsite disposal (ie. reporting not required),
while approximately 6000 tonnes may be sent to an on-site water treatment
facility prior to discharge to sewer (ie. reporting not required). This would then
indicate that 200 tonnes of waste has been released into the environment (in the
present example, the release is to atmosphere, but could also be a release direct to a
water body). If the approximate proportions of substances A and B in the waste
stream are known, the quantity of A and B released to the atmosphere can be
determined. It is important to note that you should take into account the efficiency
of any pertinent emission controls (eg. the waste may be routed through an
incinerator that destroys most, or all of substances A and B before they are released
to the atmosphere).
Alumina Refining 36
7.2 Individual Unit Process Mass Balance
The general mass balance approach described above can also be applied to individual unit
processes. This requires that information is available on the inputs (eg. flow rates,
concentrations, densities) and outputs of the unit process.
The following general equation can be used (NB. scm is an abbreviation for standard cubic
metres – refer to Section 8):
Ei = ΣQfWfiPi - ΣQoWoiPo (9)
Where:
Ei = loss rate of component i to unknown stream (kg/hr)

Qf = Volumetric flow rate of inlet stream, i (scm/hr)
Qo = Volumetric flow rate of outlet stream, o (scm/hr)
Wfi = Weight fraction of component i in inlet stream i
Woi = Weight fraction of component i in outlet stream o
Pi, Po = Density of streams i and o respectively (kg/scm)
Information on process stream input and output concentrations is generally known

because this information is required for process control. The loss Ex will be determined
through analysis of the process. You should note that it is then necessary to identify the
environmental medium (or media) to which emissions occur.
Alumina Refining 37
8.0 Monitoring
Many facilities conduct monitoring as part of the existing regulatory requirements.

Usually, the monitoring is tied directly to the conditions of an environmental licence and
will vary from site to site.
It is important to recognise that facilities also collect a range of other information (beyond
that derived from stack or liquid effluent testing), which can be used in characterising
emissions for the NPI. Typical data collected includes:
• volumetric flow rates (eg. products, wastes, wastewater treatment);

• mass flowrates;
• stream composition;
• product and waste composition; and
• production and waste quantities.
In most situations, the use of monitoring data as a basis for calculating emissions will
provide the most representative emissions information for a facility, and if available, this
data should be used for emission calculations.
Monitoring data can be expressed in a range of units. The following discussion may be of
assistance when converting monitoring results into annual emission estimates for the
purposes of the NPI. It is important to remember that the calculation of annual emissions
must also take into account the number of hours per year the source is discharging to the
environment.
Stack data is commonly presented in terms of either actual flow, or a ‘normalised’ flow.
The difference is that normalised data is standardised to a particular temperature and
pressure, typically 0°C and 1 atm respectively. However, sometimes it may be referenced
to 25°C and 1 atm. The following terms may be used when presenting data:
• acm – actual cubic metre (at actual temperature and pressure);

• scm – standard cubic metre (typically at 25°C and 1 atm, although sometimes it may be
at 20°C, or even 0°C); and
•
3
Nm – normal cubic metre (typically at 0°C and 1 atm);
It is essential to know the conditions under which the source test data is collected before
determining annual emission estimates. You should note that the measured
concentrations and flue gas flows are usually presented on source test reports at the same
conditions (ie. temperature and pressure).
Provided below are two examples of the use of sampling data to characterise annual
emissions. Example 5 is where the concentration of the compound is presented at the
same conditions as the measured flow rate. Example 6 is where the concentration and flue
gas flows are measured under different conditions.
Alumina Refining 38
Example 5
The following example relates to a situation where the concentration of the

compound is presented at the same conditions as the measured flow rate.
The following data is known:
• the flue gas flow from a stack is measured at 30 Nm3/sec;

• the measured concentration of cadmium in the flue gas is 0.01 mg/Nm3; and
• the stack operates 24 hours per day for 300 days per year.
First of all, the number of seconds per year the stack is emitting is determined:
No. seconds/year = (3600sec/hour) * (24hours/day) * (300days/year)

= 2.6 * 107 seconds/year
Using this data, the emission is derived as follows:
Emission = (30Nm3/sec) * (0.01mg/Nm3) * (2.6 * 107 sec/year)

= 7.8 kg of cadmium per year.
Example 6
If the concentration and flue gas flows are measured under different
conditions then additional calculations are required. For this example, the
following data is known:
• the flue gas flow from a stack is measured at 100 acm/sec;

• the flue gas flow from a stack is measured at 100 acm/sec;
• the stack operates 24 hours per day for 300 days per year; and
• the conditions at the stack tip are approximately 150°C and 1 atm.
Using the actual stack data, the ‘actual’ flue gas flow can be converted to a
normalised flow using a ratio of temperatures. You should note that the
temperatures must be presented using the absolute temperature scale of
Kelvin (ie. 0°C = 273 K). The conversion is then performed as follows (noting
that the actual stack conditions are 150 + 273 = 423 K):
Flue gas (Nm3/sec) = 100 acm/sec * (273/423)

= 64.5 Nm3/sec
The emission rate is then derived using the same methodology as outlined in
Example 5.
Emission = (0.01 mg/Nm3) * (64.5 Nm3/sec) * (2.6 * 107 sec/year)

= 16.8 kg of cadmium per year.
Alumina Refining 39
9.0 Emissions to Water
It is important to recognise that, for the purposes of the NPI, the following are classed as
transfers and are not required to be reported (NEPM, Clause 3(3)).
• Discharge of substances to sewer;

• Deposit of substances into landfill; and/or
• Removal of substances from a facility for destruction, treatment, recycling,
The first stage in characterising emissions to water therefore is, to identify those emissions
that are classed as transfers under the NPI. These emissions do not need to be reported
under the NPI. Other emissions however (eg. discharges to surface water bodies such as
streams and rivers), do need to be reported.
Discharges to water are highly process and site-specific. As a consequence, most facilities
perform some monitoring to characterise these emissions. While the NPI does not require
facilities to conduct monitoring to characterise emissions, it is likely that most facilities
that discharge to water will have at least some monitoring data that can be used to assist in
the characterisation of emissions. Examples relating to the application of monitoring data
for the calculation of emissions are provided below.
Where no monitoring information is available, guidance on the characterisation of

wastewater emissions is provided in the Emission Estimation Technique Manual for Sewage
and Wastewater Treatment.
Examples 7 & 8 will show how emissions can be estimated from point source discharges.
The first example is relevant for wastewater streams that have a relatively constant daily
flow rate, and the measured concentration of the relevant compound in the stream does
not vary greatly. The second example is relevant for streams that have more variable flow
rates and composition (eg. stormwater).
Alumina Refining 40
Example 7
The following information is known regarding the wastewater stream:
• the wastewater stream contains an average cadmium concentration of 500

mg/L;
• the stream is sent to an on-site wastewater treatment plant at a rate of
5 L/minute;
• the stream leaving the plant contains 25 milligrams/L of cadmium (and is
discharged to a local water body); and
• the plant operates 24 hours per day for 330 days per year.
Using the data above, determine the quantity of cadmium released from the
wastewater treatment plant.
STEP 1: Determine the annual quantity of wastewater discharged
Volume = (5 L/min) * (60 min/hour) * (24 hour/day) * (330 days/year)

= 2.4 million L/year
STEP 2: Determine the quantity of cadmium exiting the plant
Quantity (OUT) = (2.4 million L/year) * (25 mg/L)

= 60 kg/year
Therefore, based on the calculations above, 60 kg/year of cadmium is

discharged from the plant annually, and is required to be reported under the
NPI because the discharge is to a water body.
Alumina Refining 41
Example 8
This example is a little more complex than the previous one because it requires the
analysis of all monitoring data collated in a year from which an average can be
derived. In this example, samples are taken fortnightly to measure the discharge
flow from a site, as well as the cadmium levels in the discharge. The data collected
over a single year is presented in Table 22 below
The daily release is derived by multiplying the daily flow rate by the measured
level of cadmium. The annual release can be determined by multiplying the
average daily release shown in the table above, by the number of days the
wastewater treatment plant discharges per year.
For this example, the plant is assumed to be operational for 300 days per year.
Therefore, the annual emission estimate is derived as follows:
Annual release of cadmium

Ekpy,cadmium = (1.17 kg/day) * (300 days/year)
= 351 kg.
Therefore, it is estimated that 351 kg of cadmium is released from the site annually.
Alumina Refining 42
Table 22. Measurement Data
Measured Flow Cadmium Daily Release
(106 L/day) (µg/L) (kg)
1.660 918 1.52
1.576 700 1.10
1.668 815 1.36
1.760 683 1.20
1.456 787 1.15
1.360 840 1.14
1.828 865 1.58
1.696 643 1.09
1.852 958 1.77
1.656 681 1.13
1.904 680 1.29
1.724 628 1.08
1.476 807 1.19
1.568 729 1.14
1.292 964 1.25
1.208 722 0.87
1.432 566 0.81
1.288 510 0.66
1.320 630 0.83
1.288 630 0.81
1.632 652 1.06
1.768 649 1.15
1.424 695 0.99
1.560 758 1.18
1.692 658 1.11
1.948 970 1.89
AVERAGE 1.17 kg/day
Alumina Refining 43
10.0 Emissions to Land
Under the NPI, facilities are required to report their emissions to land. Emissions to land
have been defined by the NPI Implementation Working Group as:
All emissions of listed substances, except those which are directed to, and contained by,
purpose built facilities are to be reported to the NPI. This applies irrespective of whether the
substances’ fate is within or outside a reporting facility boundary. With respect to receipt of
NPI substances, such receiving facilities are to be operating in accordance with any
applicable State or Territory government requirements.
Emissions to receiving facilities such as secure landfills, sewers, and tailings dams do not
need to be reported. Similarly, the removal of a substance for transfer to another facility
for destruction, treatment, recycling, reprocessing, recovery, or purification is not required
to be reported. This means, for instance, that if an accidental release of a water-borne
pollutant is directed to a temporary bund or into a watercourse then it must be reported,
regardless of whether the emission is detectable at the boundary of the facility. If the
release is directed to and stored in a purpose built facility, (eg. a rubber lined dam), then it
does not need to be reported. However, all other emissions of NPI-listed substances except
those that are directed to and contained by purpose built receiving facilities are to be
reported under the NPI, irrespective of whether the substance’s fate is within, or outside
the reporting facility’s boundary.
To characterise emissions to land, three general EETs are discussed here:
• groundwater monitoring;
• spills; and
• on-site disposal.
10.1 Groundwater Monitoring
Some facilities conduct monitoring of groundwater to characterise emissions from the

facility. Where available, this monitoring data can be used to assist in the characterisation
of emissions. This involves determining upstream and downstream concentrations, and
using this information in conjunction with groundwater flow information, to determine
the contribution of the facility to pollutant levels in the groundwater.
In terms of meeting NPI reporting requirements, this approach is reasonable in situations

where there is no loss of substances (eg. due to evaporation) prior to the substance
entering the groundwater, and where the time between the release occurring and the
substance entering the groundwater is minimal. Therefore, for those facilities where
groundwater monitoring captures all emissions to land, such monitoring can be used as a
reasonable measure of emissions to the environment. If this is not the case, (eg. where the
rate of transmission through the soil/clay is low, or when there are other routes where
substances to land are carried off-site, such as evaporation or surface run-off), it will be
necessary to characterise these emissions using the other EETs presented in this Manual.
Alumina Refining 44
10.2 Spills
For many facilities the primary source of emissions to land will be because of spills,
including intentional spillage due to vessel washdown. Accidental spills can contribute to
emissions to land directly, to water through runoff, and to air.
Unless spilled material is routed to a secure containment facility, the quantity of material
spilled, less any material that is collected, must be reported under the NPI. In practical
terms, a log of spillages could be maintained detailing the quantities spilled, and the
composition of the spill (in particular, the quantities of NPI substances spilled). This log
could then provide the basic information required for NPI reporting.
You should note that if the spill is a volatile liquid, it is reasonable to assume that all of the
light end fraction is volatilised, and the remaining liquid is released into the ground.
However, if the liquid is not volatile and no material is collected, it is reasonable to assume
that all material is released to the land. The time, quantity of spill, temperature, and
porosity of the soil all play an important part in the estimation of release.
The evaporation rate of compounds into the atmosphere is given by the following
equation:
EVAP = 1.2 * 10-10 (MW(Pvap,i)/T) U0.78 X 0.89 Y (10)
Where:
EVAP = Evaporation rate of substance “i” (g/s)

U = Wind speed over the surface of the spill (cm/s)
X = Downwind dimension (cm)
Y = Crosswind dimension (cm)
MW = Molecular weight of substance “i” (can be obtained from Perry &
Green (1997) or
other standard chemical engineering reference texts)
Pvap,i = Vapour pressure of substance “i” at spill temperature T (dyne/cm2 =
0.0001 kPa)
T = Temperature (K)
Alumina Refining 45
Once losses to the atmosphere have been quantified, emissions to land can be estimated
using the following equation:
ERLAND,i = QttySPILL – ((time) * (Ei)) – QRemoved (11)
Where:
ERLAND,i = The emission to the land of compound “i”

QttySPILL = The quantity of compound in the liquid spilled
QRemoved = The quantity of pollutant cleaned up
Ei = The loss through evaporation of substance “i” as
estimated using the evaporation equation above
Time = The time period between when the liquid was initially
spilled, and eventual clean up
10.3 On-Site Disposal
Facilities with provision for on-site disposal of wastes will need to consider the discussion
in Section 10.0 to determine whether the disposal is classed as a transfer, or as an emission
to land under the NPI. If the disposal is not a transfer, reporting will be required under
the NPI. In a similar approach as outlined for spills, the most effective EET involves
maintaining a record of all such disposal to land and, in particular, the amount of NPI
substances contained in the material disposed of in such a manner.
Alumina Refining 46
11.0 Assumptions and Discussion
Combustion Sources
The emission factors presented in Table 14 are based on residual oil combustion. In the
absence of more appropriate data however, it may be assumed that this data also applies
to distillate oil combustion.
Trace Elements
The following discussion relates to the principle behind the mass balance approach.
USEPA (1989) suggests that because oil combustion does not generate any bottom ash, it
can generally be assumed that 100 percent of the trace elements present in the fuel are
released into the atmosphere. It is further stated that emissions of these trace elements
would be independent of combustor design and combustion sector (ie. industrial, utility
etc.). While similar comments were not made for gas combustion, it is safe to assume that
these comments would also apply to it because gas combustion does not result in the
generation of bottom ash either.
The emission factors provided in Table 6 indicate that emissions of beryllium and mercury
from residual oil combustion are lower than those from distillate oil combustion. These
emission factors have been checked with the source document (USEPA, 1998b) and are
correct. However, no explanation can be provided for this discrepancy.
Alumina Refining 47
12.0 References
1. AWMA (1992) Air Pollution Engineering Manual, Air & Waste Management Association,
Van Nostrand Reinhold, 1992.
2. Department of Agriculture, Western Australia, (1993), "Use of Bauxite Residue in the Peel-
Harvey Coastal Plain Catchment", Public Environmental Review.
3. Perry, R.H. & Green, D.W. (1997), Perry’s Chemical Engineers’ Handbook – Seventh Edition,
McGraw Hill, NY.
4. USEPA (1989), Estimating Air Toxic Emissions from Coal and Oil Combustion Sources,
Office of Air Quality Planning and Standards, US EPA, Research Triangle Park, (EPA-
450/2-89-001)
5. USEPA (1990), Air Emissions Species Manual – Volume 1 Volatile Organic Species Profiles,
Second Edition, Office of Air Quality Planning and Standards, Research Triangle Park,
(EPA-450/2-90-001a).
6. USEPA (1993), VOC/PM Speciation DBMS, Office of Air Quality Planning and
Standards, US EPA, Research Triangle Park,1993
7. USEPA (1997a), Compilation of Air Pollutant Emission Factors, Volume I: Stationary

Sources, Fifth Edition, Office of Air Planning and Standards, Office of Air Quality
Planning and Standards, US EPA, Research Triangle Park, 1995 (AirChief CD-ROM,
1997,Version 5.0)
8. USEPA (1997b) Factor Information Retrieval System (FIRE), Office of Air Quality
Planning and Standards, US EPA, Research Triangle Park, (AirChief CD-ROM,
1997,Version 5.0)
9. USEPA (1998a), Fuel Oil Combustion, March 1998 Revision to AP-42 Section 1.3.
10. USEPA (1998b), Natural Gas Combustion, September 1998 Revision to AP-42 Section 1.4
11. The following Emission Estimation Technique Manuals referred to in this Manual can
be obtained from your local environmental protection agency (see the front of the NPI
Guide for details)
• Emission Estimation Technique Manual for Combustion in Boilers;

• Emission Estimation Technique Manual for Mining;
• Emission Estimation Technique Manual for Fossil Fuel Electric Power Generation;
and
• Emission Estimation Technique Manual for Sewage and Wastewater Treatment.
Alumina Refining 48
Appendix A
(List of NPI Substances)
Alumina Refining 49
Appendix A
NPI reportable substances relevant to the Alumina Refining Industry in Australia

NPI Substance Table 1 Table 2 Alumina Refining
(ie 36 (ie 90
substances) substances)
1. acetaldehyde x x (cat 1)
2. acetic acid (ethanoic acid) x
3. acetone x x x (cat 1)
4. acetonitrile x
5. acrylamide x
6. acrylic acid x
7. acrylonitrile (2-propenitrile) x
8. ammonia (total) x
9. aniline (benzenamine) x
10. antimony and compounds x
11. arsenic and compounds x x x (cat 1, 2b)
12. benzene x x x (cat 1)
13. benzene hexachloro (HCB) x
14. beryllium and compounds x x (cat 2b)
15. biphenyl (1,1-biphenyl) x
16. boron and compounds x x (cat 1)
17. 1,3-butadiene x x
(vinyl ethylene)
18. cadmium and compounds x x x (cat 1,2b)
19. carbon disulfide x x (cat 1)
20. carbon monoxide x x x (cat2a)
21. chlorine x x(cat 1)
22. chlorine dioxide x
23. chloroethane (ethyl chloride) x
24. chloroform x x (cat 1)
(trichloromethane)
25. chlorophenols (di, tri, tetra) x
26. chromium (III) compounds x x (cat 1, 2b)
27. chromium (VI) compounds x x x (cat 1, 2b)
28. cobalt and compounds x x x (cat 1)
29. copper and compounds x x (cat 1,2b)
Alumina Refining 50
(ie 36 (ie 90
30. cumene x
(1-methylethylbenzene)
31. cyanide x x
(inorganic compounds)
32. cyclohexane x x (cat 1)
33. 1,2-dibromethane x x
34. dibutyl phthalate x
35. 1,2-dichloroethane x
36. dichloromethane x x
37. ethanol x x (cat 1)
39. 2-ethoxyethanol x x
38. 2-ethoxyethanol acetate x x
39. ethyl acetate x
40. ethyl butyl ketone x
41. ethylbenzene x x (cat 1)
42. ethylene glycol x x
(1,2-ethanediol)
43. ethylene oxide x
44. di-(2-ethylhexyl) phthalate x
(DEHP)
45. fluoride compounds x x x (cat 1,2a)
46. formaldehyde x
(methyl aldehyde)
47. glutareldehyde x x
48. n-hexane x
49. hydrochloric acid x x (cat 1, 2a)
50. hydrogen sulfide x x (cat 1)
51. lead and compounds x x x (cat 1, 2b)
52. magnesium oxide fume x x (cat 2b)
53. manganese and compounds x x (cat 1)
54. mercury and compounds x x x (cat 2b)
55. methanol x x x (cat 1)
56. 2-methoxyethanol x
57. 2-methoxyethanol acetate x
58. methyl ethyl ketone x x
59. methyl isobutyl ketone x x
Alumina Refining 51
(ie 36 (ie 90
60. methyl methacrylate x x
61. 4,4-methylene bis 2,4 aniline x
(MOCA)
62. methylenebis x
(phenylisocyanate)
63. nickel and compounds x x (cat 2b)
64. nickel carbonyl x x x (cat 2b)
65. nickel subsulfide x x x (cat 2b)
66. nitric acid x
67. organo-tin compounds x
68. oxides of nitrogen x x x (cat 2a)
69. particulate matter (pm10) x x x (cat 2a)
70. phenol x
71. phosphoric acid x
72. polychlorinated dioxins and x x (cat 2b)
furans
73. polycyclic aromatic x x x (cat 2a)
hydrocarbons (PAHs)
74. selenium and compounds x x (cat 1)
75. styrene (ethylbenzene) x x (cat 1)
76. sulfur dioxide x x x (cat 1,2a)
77. sulfuric acid x x x (cat 1)
78. 1,1,1,2-tetrachloroethane x
79. tetrachloroethylene x x
80. toluene (methylbenzene) x x
81. toluene-2,4-diisocyanate x
82. total nitrogen x x x (cat 3)
83. total phosphorus x x x (cat 3)
84. total volatile organic x x (cat 2a)
compounds
85. 1,1,2-trichloroethane x
86. trichloroethylene x x
87. vinyl chloride monomer x
88. xylenes x x x (cat 1)
(individual or mixed isomers)
89. zinc and compounds x x (cat 1)
Alumina Refining 52
Appendix B
(Process Description and Flow Diagram)
Alumina Refining 53
APPENDIX B
PROCESS DESCRIPTION
The Refining Process
Metallic mineral processing typically involves the mining of ore from either open pit or
underground mines, the crushing and grinding of ore, the separation of valuable minerals
from matrix rock through various concentration steps, and at some operations, drying,
calcining, or pelletizing of concentrates to ease further handling and refining.
The number of crushing steps necessary to reduce ore to the proper size varies with the
type of ore. Softer ores, such as some uranium, bauxite, and titanium/zirconium ores,
require little or no crushing. Final comminution of both hard and soft ores is often
accomplished by grinding operations using media such as balls or rods of various
materials. Grinding is most often performed with an ore/water slurry, which reduces
particulate matter (PM) emissions to negligible levels.
After final size reduction, the beneficiation of the ore increases the concentration of
valuable minerals by separating them from the matrix rock. Various physical and
chemical processes are used to concentrate the mineral. Most often, physical or chemical
separation is performed in an aqueous environment that eliminates PM emissions,
although some ferrous and titaniferous minerals are separated by magnetic or electrostatic
methods in a dry environment. The concentrated mineral products may be dried to
remove surface moisture.
Alumina is produced from bauxite by the Bayer Process. In the Bayer Process, aluminum
hydroxides or hydrates are selectively separated from other components by extracting
them with sodium hydroxide to form sodium aluminate. Alumina is then precipitated
from the sodium aluminate solution, washed, and calcined. The process is shown in Figure
A.1.
To prepare bauxite for processing, mined ore is crushed and ground in ball mills to a
finely divided state. Most bauxite as mined has a low moisture content. If the moisture
content is high, then the bauxite must be dried in rotary kilns before it is sent to storage.
The drying operation emits significant amounts of bauxite dust.
To produce high purity alumina suitable for aluminum reductions cells, finely divided
bauxite containing 30-70% alumina is slurried with sodium hydroxide solution and
reacted at high temperature and pressure in reactors called digesters. Sodium aluminate is
formed leaving behind most of the silicon, iron, titanium, and calcium oxides as insoluble
components in the solid waste residue. This is formed according to the following general
equation:
Al2O3 * (H2O) + 2NaAlO2 + (1 + x) H2O
The hot slurry is usually cooled by flash evaporation, producing steam that is used to heat
incoming slurry. Next, the slurry is processed in a series of clarification steps designed not
only to separate the solid residue from the liquor, but also to rid the solution of the
Alumina Refining 54
impurities that would lower the quality of the aluminum when the alumina later is
electrolysed. These impurities are mainly oxides of silicon and iron.
If the bauxite contains coarse material (mainly sand), it is first removed from the slurry in
hydrocyclones, and starch or some settling agent is added to the overflow before it enters
a clarifier. Starch promotes agglomeration and settling of the fine particles, and the
relatively clear overflow from the clarifier is filtered in either filter presses, or sand filters
to remove any remaining suspended solids. The clarifier underflow is then washed in
thickeners to remove as much caustic as possible before it is pumped to a bauxite residue
pond. The filtrate containing sodium aluminate, now at 50°C to 70°C, is processed in
precipitators where aluminum hydroxide crystalises and precipitates as shown in the
following
2NaAlO2 + 4H2O = 2Al (OH)3 + 2NaOH
After precipitation, the slurry containing trihydrate crystals is sent to classification, where
the product is separated according to crystal sizes. The coarse product is washed to
remove excess sodium hydroxide, dewatered on vacuum filters, and sent to calcination.
The finer crystals are recycled to the precipitation process as seed, thereby providing
nucleation sites for precipitation to occur. Spent liquor from the precipitators is recycled to
the digesters.
The coarse alumina is calcined in rotary kilns or fluid-bed calciners at about 1800oF.
During calcination, water (mechanically and chemically bound) is driven off. Calcination
produces hot flue gases containing alumina and water vapour, and the usual types of
control equipment consist of cyclonic separators followed by ESPs. The control equipment
not only minimises air pollution, but recovers valuable product as well. Calcined alumina
is stored for shipment to the smelter as feedstock for the aluminum electrolytic cells.
Alumina Refining 55
F ig u r e B 1 – B a y e r P r o c e s s F lo w s h e e t
[A d a p te d fr o m A ir P o llu tio n E n g in e e r in g
M a n u a l
Alumina Refining 56
Alumina Refining 57

Australia Falref

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Australia Falref

Uploaded by

Copyright:

Available Formats

1DWLRQDO3ROOXWDQW,QYHQWRU\

First Published in March 1999

1.0 INTRODUCTION ................................................................................................. 1

2.0 REPORTABLE SUBSTANCES............................................................................ 2

3.0 EMISSION ESTIMATION TECHNIQUES...................................................... 4

9.0 EMISSIONS TO WATER..................................................................................... 40

10.0 EMISSIONS TO LAND........................................................................................ 44

APPENDIX A: NPI SUBSTANCES RELEVANT TO ALUMINA REFINING ...... 49

APPENDIX B: PROCESS DESCRIPTION AND FLOW DIAGRAM...................... 53

LIST OF FIGURES & TABLES

Figure 1. Raw Materials Handling.......................................................................................9

Table 1. Activities with the Potential to Trigger NPI Reporting ............................. 2

Alumina Refining iii

EET MANUAL: Alumina Refining

HANDBOOK: Alumina Production

ANZSIC CODE: 2721

The alumina refining activities covered by this Manual include:

• Raw material handling and storage;

• Whether you are required to report under the NPI; and

Step 1: Identify activities that trigger thresholds

Table 1. Activities with the Potential to Trigger NPI Thresholds. a

Step 4: Identify appropriate EETs for use in quantifying emissions

Additional guidance on the interpretation of ‘transfers’ as it applies to alumina refining is

Category 1 and 1a Substances

• a Category 1 listed substance is only reportable if 10 tonnes or more of the substance is

The four types described in The NPI Guide are:

• sampling or direct measurement;

3.1 Use of Emission Factors

Ekpy,i = [A * OpHrs] EFi * [1 - (CEi/100)] (1)

Ekpy,i = emission rate of pollutant i, kg/yr

3.2 Mass Balance Techniques

3.3 Software Models

• Section 6: Emissions to Air;

(a) deposit of a substance into landfill; or

4.2 Using this Manual

Step 2: Locate the EETs

Air Emissions: Section 6

Section 6.1: Combustion (Section 6.1.3 deals with trace metals);

Water Emissions: Section 9

Bauxite storage has the potential for generation of diffuse runoff.

Land Emissions: Section 10

4.3 Alumina Refining Inputs/Outputs

FIGURE 3: DRYING AND CALCINING

Formation of dried AIR

FIGURE 6: WATER MANAGEMENT

Seawater Water Use and Treatment WATER

Section 5.1: Combustion sources

5.1 Combustion Sources

5.2 Aggregate Handling and Storage

• Unloading or “transporting to processing site” via conveyer;

Table 3. NPI Emissions from Bauxite Storage and Handling

5.2.2 Limestone and other Aggregate

Potential emissions of NPI substances are provided in Table 4.

Table 4. NPI Emissions from Lime/Limestone Storage and Handling

Table 5. NPI Emissions from Bulk Chemical Storage

5.4 Bauxite processing

Table 7. NPI Emissions from Digestion

• Passage of slurry through hydrocyclones to remove grit;

Table 8. NPI Emissions from Precipitation and Clarification

• washed to remove excess sodium hydroxide;

Table 9. NPI Emissions from Calcining

5.6 Spent Process Material Storage

• red mud from precipitator and clarifier;